N-phosphoryl and n-phosphonyl amidines

ABSTRACT

WHEREIN R1 represents phenyl, or phenyl mono- to trisubstituted by halogen, mono- or disubstituted by C1-C4-alkyl, C1-C4alkylthio, nitro, cyano or trifluoromethyl, or monosubstituted by C1-C4-carbalkoxy, R2 represents methyl, methoxy, ethyl, ethoxy or phenyl, R3 represents hydrogen or methyl, R4 and R5 represent methyl, ethyl, n-propyl, isopropyl or allyl, X and Y represent oxygen or sulphur, or R4 and R5 with the nitrogen atom to which they are bound form the morpholino, piperidino or pyrrolidino ring, or R3 with R4 or R5 forms a 5- or 6-membered saturated ring, whereby then the group R4 or R5 not participating in the ring formation represents methyl or ethyl, A PROCESS FOR THEIR MANUFACTURE AND THEIR USE FOR THE CONTROL OF PESTS, ESPECIALLY FOR THE CONTROL OF PHYTOPATHOGENIC NEMATODES, ARE DISCLOSED.   Compounds of the formula

United States Patent [191 Beriger et al.

May6, 1975 l l N-PHOSPHORYL AND N-PHOSPHONYL AMIDINES [73] Assignee:Ciba-Geigy Corporation, Ardsley,

[22] Filed: Mar. 13, 1973 [21] Appl. No.: 340,805

[30] Foreign Application Priority Data Mar. [7, I972 Switzerland .04054/72 {52] US. Cl. 260/240 G; 260/551 P; 260/940;

260/941; 260/945; 424/200; 424/2l0; 424/220 [5| I Int. Cl. C07! 9/24[58] Field of Search 260/240 G, 945, 940, 941

[56] References Cited UNlTED STATES PATENTS 3.l2l,084 2/1964 Winberg260/968 X 3,80l 679 4/1974 Hoffman et al i t 260/945 FOREIGN PATENTS ORAPPLlCATlONS l,223 38l 8/[966 Germany 260/945 Primary Examiner-John D.Randolph Attorney, Agent, or FirmHarry Falber; Frederick H Rabin [57]ABSTRACT Compounds of the formula )1 R ll 11 2 P1-::-on R 1 l R whereinR, represents phenyl. or phenyl monoto trisubstituted by halogen, monoordisubstituted by C -C -alkyl, C -C alkylthio, nitro, 'cyano ortrifluoromethyl, or monosubstituted by C -C -carbalkoxy, R representsmethyl, methoxy, ethyl, ethoxy or phenyl, R represents hydrogen ormethyl, R, and R represent methyl, ethyl, n-propyl,

isopropyl or allyl, X and Y represent oxygen or sulphur, or R and R withthe nitrogen atom to which they are bound form the morpholino,piperidino or pyrrolidino ring, or R with R or R forms a 5- or6-membered saturated ring, whereby then the group R or R notparticipating in the ring formation represents methyl or ethyl, aprocess for their manufacture and their use for the control of pests,especially for the control of phytopathogenic nematodes, are disclosed.

22 Claims, No Drawings N-PHOSPHOR\L AND N-PHOSPHONYL AMIDINES Thepresent invention relates to N-phosphoryl amidines, N-phosphorothioylamidines, N'phosphonyl amidines and N-phosphonothioyl amidines, toprocesses for their production, and to their use for pest control.

The amidines correspond to the formula R Y I wherein R representsphenyl, or phenyl monoto trisubstituted by halogen. monoor disubstitutedby C -C alkyl. C -C -alkylthio, nitro, cyano or trifluoromethyl, ormonosubstituted by c -C -carbalkoxy,

R represents methyl, methoxy, ethyl, ethoxy or phenyl,

R represents hydrogen or methyl,

R and R represent methyl, ethyl, npropyl, isopro- The compounds offormula I preferred on account of their action are those wherein R,represents the groups 3-methyl-4- methylthiophenyl, 4nitrophenyl,3-methyl-4- 5 nitrophenyl, 2,5-dichloro-4-bromophenyl, 2,5-dichloro-4-iodophenyl, 4-methylphcnyl, 2,4- dibromo5chlorophenyl,2,4,5-trichlorophenyl, 3-chlorophenyl, 3-trifluoromethylphenyl, 4-methylthiophenyl, 4-chlorophcnyl or 4- IO cyanophenyl.

R represents methyl, methoxy, ethyl or ethoxy, R represents hydrogen, Rand R represent methyl or ethyl, or R and R together with the nitrogenatom to which they are bound form the morpholino, piperidino orpyrrolidino ring,

X represents sulphur, and

Y represents oxygen.

Compounds of formula I forming a particularly preferred group are suchcompounds wherein R represents the 3-methyl-4-methylthio group,

R represents methyl, methoxy, ethyl or ethoxy,

R represents hydrogen,

R and R represent methyl or ethyl,

pyl or allyl, X represents sulphur, and X and Y represent oxygen orsulphur, or Y represents oxygen. R and R with the nitrogen atom to whichthey are The compounds of formula I can be produced by the bound formthe morpholino, piperidino or pyrfollowing methods known per se:

X 2 Ii R 0 at 1) P-N'H r"l1 MW. 1

R. Y R .0 i it, 2 b R ,J (1 5 rolidino ring, or Reaction temperature-5()C to +lOOC r R ll R o t. lonal l a) /PL'l Nli -fl- J7 I r R'Y Ractd-btndtng i R agent R with R or R forms a 5- or 6-membered saturatedReaction temperature C to +1 00C ring, whereby then the group R or R notpartici- 50 Conversion t 0 it )1 /j tfullisfl It b'..\

h 0 :1. R R

* f) V .l 5

(M11; (my (M111,

pating in the ring formation represents methyl or In formulae II toVlll, the symbols R to R X and Y ethyl. have the meanings given forformula I, R stands for C,- The C -C -alkyl, C -C -aIkylthio and C1-C C-alkyl, and Hal for chlorine, bromine. iodine or for carbalkoxy groupsas substituents on the phenyl nuthe radical ofa sulphuric acid ester.cleus of the radical R can be branched or straight- Applicableacid-binding agents are: tertiary amines, Chaifl- Examples of Such g pflrci y yl, eg trialkylamines, pyridine, pyridine bases or dialkpropyl,n propyl, n-, i-, sec.-, tert.-buty'l, methylthio, ethylthio,n-propylthio. isopropylthio, n-butylthio, carbomethoxy, carbethoxy andisopropoxycarbonyl.

By halogen is meant fluorine, chlorine, bromine or iodine, particularlychlorine, bromine or iodine.

ylanilines; inorganic bases such as hydrides or hydroxides; carbonatesand bicarbonates of alkali metals and alkaline-earth metals. Theprocesses 1 and 2 are carried out at normal pressure, with the exclusionof moisture, and in inert solvents or diluents.

Suitable inert solvents or diluents are, for example. ethers andethereal compounds such as diethyl ether dipropyl ether dioxane.tetrahydrofuran'. aliphatic, ar omatic as well as halogenatedhydrocarbons. particularly benzene toluene Xylencs chloroform orchlorobenzene; and nitriles such as acetonitrile.

The starting materials of formulae II to V are in some cases knowncompounds (cpl e.g. DOS, 2,019,597 or can be produced by methodsanalogous to known methods. Thus, the methods of production of the amideacctals required in the case of process I are described in Zeitschriftfur Chemie 9. 20l i969) and the production of (thio)phosphoric acidamides in Houben Weyl. Methoden der oranischen Chemie (Methods ofOrganic Chemistry). Vol. Phosphorus II.

The active substances of formula I are suitable for the control of themost diverse animal pests. The said ac tive substances can be used, forexample, against all development stages, such as eggs. larvae, nymphspupae and adults of insects and members of the order acarina, such asmites and ticks They can be used. for example, against the followinginsects or members of the order aearina:

Insects of the families: Tettigonidae. Gryllidac, Gryllotalpidae,Blattidae, Reduviidae. Phyrrhocoridae, Cimicidae. Delphacidae, AphididaeDiaspididae. Pseudococcidae Scarabaeidae, Dermestidae, CoccinellidaevTenebrionidae. Chrysomelidae, Bruchidae Tineidae. NoctuidaeLymantriidae, Pyralidae Galleridae Culicidae, Tipulidae, Stomoxydae,Muscidae, Calliphoridae, Trypetidae and Pulicidae; as well as acarids ofthe families: lxodidae Tetranychidae and Dermanyssidae,

The insecticidal or aearicidal action can be substantially broadened andadapted to suit the given circum stances by the addition of otherinsecticides and/or acaricides. Suitable additives are. for example, thefol lowing active substances:

Organic phosphorus compounds Bis-0.0-diethylphosphoric acid anhydridelTEPPl Dimethyl-( 2 ,2,2trichlorol -hydroxyethyl phosphonate(TRICHLORFON) l .Z-dibromo2 2dichloroethyldimethy[phosphate (NALED)2,2-dichlorovinyldimethylphosphate (DICHLORVOS) Z-methoxycarbamyll-methylvinyldimethylphosphate (MEVINPHOS) Dimethyll -methyl-2-(methylcarbanioyl vinylphosphate cis (MONOCROTOPHOS)3-(dimethoxyphosphinyloxy)-N,N-dimethyl-cis crotonamide (DlCROTOPHOS)2-chloro-2-diethylcarbamoyll -methylvinvldimethylphosphate(PHOSPHAMIDON) 0,0-dicthyl-O( or S )Z( ethylthio -ethylthiophosphatc(DEMETON) S-ethylthioethyHLU-dimethyl-dithiophosphate OMETON)0,0diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) 0.0-diethyl-S-Zt ethylthio )ethyldithiophosphate SULFOTON) 0,0-dimethvlS-Z-(ethylsulphinyl )ethylthiophosphate (OXYDEMETON METHYL)0.0-dimethylS'( l.2-dicarbethoxyethyldithiophosphate (MALATHION)0.0.0,0tetraethyl-S,S'-methylene bisdithiophosphate (ETHION) O-ethyl-SSdipropyldithiophosphatc (THI- FOR-0,0-dimethyl-O-p-nitrophenylthiophosphate (PA- RATHlON-METHYL)0,0-diethvl-O-p-nitrophenylthiophosphate (PARA- THION)O-ethyLO-p-nitrophenylphenylthiophosphate (EPN) O,()-dimethyl-O-(4-nitro-m-tolyl )thiophosphate (FEN lTROTHlON) O O-dimethyl-O 2.45-trichlorophenylthiophosphate RONNEL) O-ethyl-(LZ4,5-trichlorophenylethylthiophosphate (TRICHLORONATEJ0,0-dimethyl-O-2,5-diehloro-4-bromophenylthiophosphate (BROMOPHOS)O,()-dimeth vl-O-( 2 S-dichloro-4 iodophenyl thiophosphate (JODOFENPHOS)4-tert.butyl-2-chlorophcnyl-N-methyl-O- methylamidophosphate (CRUFOMATE)0,0-dimethyl-O-( 3-methyl-4-methylmercaptophenyl thiophosphate(FENTHION) lsopropylamino-O-ethyl-O-(4-methylmcrcapt0-3- methylphenyl)-phosphate 0.0-diethyl-O-pmethylsulphinyl )phenylthiophosphate (FENSULFOTHION) O-p- )dimethylsulphamido )-penyl-0,0-dimethylthiophosphatc(FAMPHUR) 0,0,0.O'-tetramethyl-0,0-thiodi-p-phenylenethiophosphateO-ethyl-S-phenyl-ethyldithiophosphate 0,0-dimethyl-O-( a-methylbenzyl-3-hydroxycrotonyl phosphate Z-chloro l 2 4-dichlorophenyl)vinyldiethylphosphate (CHLORFENVINPHOS) 2-chlorol 2,4.5-triehlorophenyl)vinyldimethylphosphate O Z-ehlorol 2,5-dichlorophenyl ]vinyl-0,0diethylthiophosphate Phenylglyoxylonitriloximc-0.0-diethylthiophosphate(PHOXIM) O O-diethylO-( 3-chloro-4-methyl-2-oxo-2-H- l benzopyran-7'yl)-thiophosphate (COUMAPHOS) 23-p-dioxandithiol-S,S-bis(0,0-diethyldithiophosphate) (DIOXATHION)S-l(6-chloro-2-oxo-3-benzoxazolinyl)methyl10.0- diethyldithiophosphate(PHOSALONE) Z-tdicthoxyphosphinylimino)-1,3-dithiolane 0.0-dimethyl-S-[Z-methoxy-l ,3,4-thiadiazol-5( 4H onyH 4 )-methyl ldithiophosphate0.0-dimethyl-S-phthalimidomcthyl-dithiophosphate (IMIDAN)0,0-diethyl-()-( 3,5 ,b-triehloro-Z-pyridyl )thiophosphate OO-diethyl-O-lpyrazinylthiophosphate ZlNl 0.0-dieth vl-O-( 2-isopropyl4-methyl-6-pyrimidyl )thiophosphate (DIAZINON) O O-diethyl-O-(2-quinoxalyl )thiophosphate 0.0-dimeth vl-S-( 4-oxo'l.2,3benZotriazin-3( 4H vlmethyl )-dithiophosphate (AZINPHOSMETHYL)0,0-dieth vl-S-( 4-oxo-l 2.3-benzotriaZin-3( 4Hylmethyl)-dithiophosphate (AZINPHOSETHYL) S-l(4,6-diamino-s-triazin-Z-yl )methyl]-O O- dimethyldithiophosphate (MENAZON) (THIONA- 3-dimethylamino methyleneiminophenyl-N- methylcarbamate(FORMETANATE) and its salts l -methylthio-ethylimino-N-methylcarbamateTHOMYL) Z-methylcarbamoyloximino-1,3-dithiolane-methyl-2-methylcarbamoyloximino-l ,3-oxythiolane 2-(l-methoxy-Z-propoxy )phenyl-N-methylcarbarnate 2-(1-butin-3-yl-oxy)phenyl-N-methylcarbamate l-dimethylcarbamyll-methylthio-O-methylcarbamylformoxine l-dimethylcarbamyll-methylthio-O-methylcarbamylforrnoximel-(2'-cyanoethylthio-O-methylcarbamyl-acetaldoximel-methyIthio-O-carbamyl-acetaldoxime O-( 3-sec.butylphenyl)-N-phenylthi0-N- methylcarbamate 2,5-dimethyl-l ,3-dithiolane-2-(O-methylcarbamyl aldoxime) O-E-diphenyl-N-methylcarbamate2-(N'methylcarbamyl-oximino)-3-chlorobicyclo[ 2.2. l ]heptane2(N-methylcarbamyl-oximino)-bicyclo[ 2.2.1 lheptane3isopropylphenyl-N-methyl-N-chloroacetalcarbamate3-isopropylphenyl-N-methyl-N-methylthiomethylcarbamate O-(2,2-dimethyl-4-chloro-2,3-dihydro-7- benzofuranyl)-N-methylcarbamateO-(2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl)-N- methylcarbamateO-naphthyl-N-methyl-N-acetal-carbamate N-methyl-N-acetal-carbamate0-5,6,7,8-tetrahydronaphthyl-Nmethyl-carbamate3-isopropyl-4-methylthio-phenyl-N-methylcarbamate3,5-dimethyl-4-methoxy-phenyl-N-methylcarbamate3-methoxymethoxy-phenyl-N-methylcarbamate3-allyloxyphenyl-N-methylcarbamateZ-propargyloxymethoxy-phenyl-N-methyl-carbamate2-allyloxyphenyl-N-methyl-carbamate4-methoxycarbonylamino-3-isopropylphenyl-N-methyl-carbamate3,5-dimethyl-4-methoxycarbonylamino-phenyl-N methyl-carbamateZ-y-methylthiopropylphenyl-N-methyl-carbamate3-(a-methoxymethyl-Z-propenyl)-phenyl-N-methylcarbamate2-chloro-5-tert.-butyl-phenyl-N-methyl-carbamate4-(methyl-propargylamino-3,5xylyl-N-methylcarbamate 4-(methyl-'y-chloroallylamino )-3 .5-xylyl-N-methylcarbamate4-(methyl-B-chloroallylamino)-3,5-xylyl-N-methyl carbamatel-(B-ethoxycarbonylethyl J-3-methyl-5-pyrazolyl-N,N- dimethylcarbamate3-methyl-4-(dimethylamino-methylmercaptomethyleneiminoJphenyl-N-methylcarbamatel,3-bis( carbamoylthio )-2-( N,N-dimethylamino)- propanehydrochloride5,5-dimethylhydroresorcinoldimethylcarbamate2-[cthyl-propargylamino]-phenyl-N-methylcarbamate2-lmethyl-propargylaminol-phenyl-N- methylcarbamate 2-[dipropargylaminol-phenyl-N-methylcarbamatc 4-[ dipropargylaminoj3-tolyl-N-methylcarbamate4-[dipropargylamino1-3,5-xylyl-N-methyIcarbamate -naphthyl- 2-allyl-isopropylarr'iino ]-phenyl-N-methylcarbamate3-[allyl-isopropylamino]-phenyl-N-methylcarbamate ChlorinatedHydrocarbons 'y-hexachlorocyclohexane (GAMMEXANE: LINDAN; 'y HCH]l,2,4,5,6,7,8,8-octachloro-3(1,4,7,7a'tetrahydro-4,7- methylene indane[CHLORDAN] 1,4,5 ,6,7,8,S-heptachloro,3a,4,7,7a-tetrahydro-4,7-methylene indane [HEPTACHLORJ 1,2,3,4,10,10-hexachloro-l,4,4o1,5,8,8a-hexahydroendol ,4-exo-5,S-dimethanonaphthalene [ALDRIN]l2,3,4,10,lO-hexachloro-6,7-epoxyl ,4,4a,5,6,7,8,8aoctahydro-exol,4-endo-5 ,8-dimethanonaphthalene [DIELDRIN] 123,4, 1 O,lO-hexachloro-ilepoxy-l,4,4a,5,6,7,8,8aoctahydro-endo-endo-S,8-dimethanonaphthalene [EN- DRIN].

In the forefront are the good nematocidal properties of the compounds offormula I. They can be used, for example, for the control of thefollowing phytopathogenic nematodes: Meloidogyne spp., Heterodera spp.,Ditylenchus spp., Pratylenchus spp., Paratylenchus spp.. Anguina spp.,Helicotylenchus spp., Tylenchorhynchus spp., Rotylenchulus spp.,Tylenchulus semipen etrans, Radipholus sililis, Belonolaimus spp.,Trichodorus spp., Longidorus spp., Aphelenchoides spp., Xiphinema spp,and Rhadinaphelenchus spp..

The compounds of formula I can be used on their own or together withsuitable carriers and/or additives. Suitable carriers and additives maybe solid or liquid, and correspond to the substances common informulation practice, such as, eg natural regenerated substances,solvents, dispersing agents, wetting agents, adhesives, thickeners,binders and/or fertilisers.

For application, the compounds of formula I can be processed into theform of dusts, emulsion concentrates, granulates, dispersions, sprays,or solutions, the formulation of these preparations being effected in amanner commonly known in practice. Also to be mentioned are cattle dipsand spray races, in which aqueous preparations are used.

The agents according to the invention are produced in a manner known perse by the intimate mixing and- /or grinding of active substances offormula I with the suitable carriers, optionally with the addition ofdispersing agents or solvents which are inert to the active substances.The active substances can be obtained and used in the followingpreparation forms: solid preparations:

dusts, scattering agents, granulates, coated granulates, impregnatedgranulates and homogeneous granulates', liquid preparations:

:1. water dispersible active substance concentrates:

wettable powders, pastes. emulsions;

b. solutions.

The solid preparations (dusts, scattering agents) are produced by themixing of the active substances with solid carriers. Suitable carriersare, e.g. kaolin, talcum, bole, loess, chalk, limestone, groundlimestone. attapulgite, dolomite, diatomaceous earth, precipitated silicic acid, alkaline earth silicates, sodium and potassium aluminiumsilicates (feldspar and mica), calcium and magnesium sulphates,magnesium oxide, ground synthetic materials, fertilisers such asammonium sul phate, ammonium phosphate. ammonium nitrate. urea, groundvegetable products such as bran. bark dust. sawdust. ground nutshclls.cellulose powder. residues of plant extractions. active charcoal, etc.alone or in admixture with each other.

Granulates can be very easily prepared by a process in which an activesubstance of formula 1 is dissolved in an organic solvent. the thusobtained solution applied to a granulated mineral. e.g. attapulgite, SiOgranicalcium. bentonite. etc.. and the organic solvent then evaporatedoff.

It is possible also to produce polymer granulates'. in this case theactive substances of formula l are mixed with polymerisable compounds(urea/formaldehyde; dicyandiamide/formaldehydc; melamine/formalde hydc.or others); polymerisation is then carefully carried out in a mannerwhich leaves the active substances unaffected, and granulation performedactually during the gel forming process. It is more favourable. however.to impregnate finished porous polymer granules (urea/- formaldehyde,polyacrylonitrile. polyester and others), having a specific surface areaand a favourable predeterminable adsorption/desorption ratio. with theactive substances. e.g. in the form of their solutions (in a lowboilingsolvent), and to then remove the solvent. Polymer granulates of thiskind can be also sprayed in the form of microgranulates. having bulkweights of preferably 300 g/litre to 600 g/litre, with the aid of sprayapparatus. Spraying can be carried out over extensive areas of usefulplant crops by the use of aeoplancs.

Granulates can also be obtained by the compacting of the carriermaterial with the active substances and additives. and a subsequentreducing operation.

Moreover. it is possible to add to these mixtures additives stabilisingthe active substance and/or nonionic, anion-active and cation-activesubstances which improve. e.g. the adhesiveness of the active substanceson plants and parts of plants (adhesives and agglutinants). and/orensure a better wettability (wetting agents) as well as dispersibility(dispersing agents).

The following substances are. for example, suitable: olein/lime mixture,cellulose derivatives (methyl cellulose. carboxymethyl cellulose),hydroxyethylene glycol ethers of monoalkyl and dialkyl phenols having 5to ethylene oxide radicals per molecule and 8 to 9 carbon atoms in thealkyl radical. ligninsulphonic acid. the alkali metal and alkaline-earthmetal salts thereof. poly' ethylene glycol ethers (carbowaxcs). fattyalcohol polyglycol ethers having 5 to Z0 ethylene oxide radicals permolecule and 8 to 18 carbon atoms in the fatty alcohol moiety.condensation products of ethylene oxide. propylene oxide,polyvinylpyrrolidones. polyvinyl alcohols, condensation products of ureaand formaldehyde. as well as latex products.

Water-dispersible concentrates of active substances. ie. \vettablepowders. pastes and emulsion concentrates. are agents which can bediluted with water to obtain any desired concentration. They consist ofactive substance. carrier. optionally additives which stabilise theactive substance. surface-active substances. and anti-foam agents and.optionally. solvents.

The wettable powders and pastes are obtained by the mixing and grindingof the active substances with dis' persing agents and pulverulentcarriers. in suitable de' vices. until homogeneity is obtained. Suitablecarriers are, e.g. those previously mentioned in the case of solidpreparations. It is advantageous in some cases to use mixtures ofdifferent carriers. As dispersing agents it is possible to use. e.g,:condensation products of sulphonated naphthalene and sulphonatednaphthalene derivatives with formaldehyde. condensation products ofnapthalene or of naphthalenesulphonic acids with pheno] andformaldehyde. as well as alkali, ammonium and alkaline-earth metal saltsof ligninsulphonic acid. also a]kylarylsulphonates. alkali metal saltsand alkalineearth metal salts of dibutyl naphthalenesulphonic acid.fatty alcohol sulphates such as salts of sulphated hexadecanols.heptadecanols. octadecanols. and salts of sulphated fatty alcohol glycolethers, the sodium salt of oleyl methyl tauride. ditertiary ethyleneglycols, dialkyl dilauryl ammonium chloride. and fatty acid alkalimetaland alkaline-earth metal salts.

Suitable anti-foam agents are, eg. silicones.

The active substances are so mixed, ground. sieved and strained with theabove mentioned additives that the solid constituent in the case ofwettable powders has a particle size not exceeding 0.02 to 0.04 mm. andin the case of pastes not exceeding 003 mm. For the preparation ofemulsion concentrates and pastes, dispersing agents are used such asthose mentioned in the preceding paragraphs, organic solvents and water.Suitable solvents are. e.g. alcohols. benzene. xylene. toluene.dimethylsulphoxide, and mineral oil fractions boiling in the range of120 to 350C. The solvents must be practically odourless. nonphytotoxic.and inert to the active substances.

Furthermore, the agents according to the invention can be used in theform of solutions. For this purpose. the active substance, or severalactive substances, of the general formula I is dissolved in suitableorganic solvents. solvent mixtures, or water. As organic solvents it ispossible to use aliphatic and aromatic hydro carbons. their chlorinatedderivatives, alkylnaphthalenes, mineral oils on their own or inadmixture with each other.

The content of active substance in the above described agents is between().l and percent; it is to be mentioned in this connection that in thecase of application of the agents from an aeroplane. or by means of someother suitable application devices, concentrations of up to 99.5 percentcan be used. or even the pure active substance.

The active substances of formula I can be prepared, eg. as follows:

Dusts The following substances are used for the preparation of a) a 5percent dust, and b) a 2 percent dust:

a. 5 parts of active substance 95 parts of talcum.

b. 2 parts of active substance 1 part of highly dispersed silicic acid97 parts of talcum.

The active substances are mixed and ground with the carriers.

Granulate The following substances are used to produce a 5 percentgranulate:

5 parts of active substance.

02. parts of cpichlorhydrin.

0.25 parts of cctyl polyglycol ether.

3.50 parts of polyethylene glycol.

9i parts of kaolin (particle size 0.3 0.8 mm).

The active substance is mixed with epichlorhydrin and dissolved with 6parts of acetone; the polyethylene glycol and cctyl polyglycol ether arethen added. The thus obtained solution is sprayed on to kaolin, and theacetone subsequently evaporated in vacuo.

Wettable powder The following constituents are used for the preparationof a) a 40 percent, b) and c) a 25 percent, and cl) a l percent wettablepowder:

a. 40 parts of active substance,

parts of sodium lignin sulphonate.

1 part of sodium dibutyl-naphthalene sulphonate,

54 parts of silicic acid.

b. 25 parts of active substance.

4.5 parts of calcium lignin sulphonate l.9 parts of Champagnechalk/hydroxyethyl cellulose mixture (lzl 1.5 parts of sodium dibutylnaphthalene sulphonate,

[9.5 parts of silicic acid,

l9.5 parts of Champagne chalk,

28.l parts of kaolin.

c. 25 parts of active substance,

EXAMPLE l a. N,N-dimethyl-N '-O-methyl-O-( 3 ,6-dichloro-4-iodophenyl)-thionophosphoryl-formamidine An amount of g ofN,N-dimethylformamidedimethylacetal is poured over 25 g of y (i;

dichloro-4-iodophenylJ-thiophosphoric acid amide, and the whole shakenuntil a clear solution is obtained.

parts of iSOOCtylphenoxyrelyoxyethylene All volatile fractions are thendistilled off at 50C/l ethanol, Torr to leave 28.6 g of the compound ofthe formula 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixturel1] 8.3 parts of sodium aluminium silicate, S

l6.5 parts of kieselguhr, H l

46 parts of kaolin. (CH A c c I d. 10 parts of active substance, 5 Z inI i 3 parts of a mixture of the sodium salts of saturated CH 0 Cl fattyalcohol sulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture being then ground in the appropriate mills androllers. Wettable powders are obtained which can be diluted with waterto give suspensions of any desired concentration. Emulsifiableconcentrates The following substances are used to produce a) a 10percent and b) a 25 percent emulsifiable concentrate:

a. 10 parts of active substance, 3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylarylsulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene.

b. 25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

l0 parts of an alkylarylsu[phonate/fatty alcohol polyglycol ethermixture 5 parts of dimethylformamide,

57.5 parts of xylene.

CHO

as viscous resin, which after a few days solidifies in crystalline form;M.P. 87 92C. b. N-[O-( 2,5-dichloro-4-iodophenyl )-O-methylthionophosphoryll-piperidinyl-formimide l 2.4 g of O-methyl-O-( 3,6-dichloro-4- iodophenyl)thiophosphoric acid amide is stirred with acrystalline form. After cooling to 0C, the product is filtered off andwashed with methanol to obtain 1 2 g of the compound of the formula MP.150 l52C.

The following further compounds of formula I are pro duced in ananalogous manner.

EXAMPLE 2 Insecticidal stomach poison action Cotton and potato plantswere sprayed with a 0.05 percent aqueous active-substance emulsion(obtained from a 10 percent emulsifiable concentrate). After the dryingof the obtained coating, Dysdercus fasciatus nymphs were placed on thecotton plants. and Colorada beetle larvae (Leptinotarsa decemlineata) onthe potato plants. The test was carried out at 24C with 60 percentrelative humidity.

The compounds according to Example 1 exhibited in the above test a goodinsecticidal stomach poison action against Dysdercus fasciatus andLeptinotarsa decemlincata,

EXAMPLE 3 Ascaricidal action A) Action against mites (Tetranychusurticae) In order to test the acaricidal action, bean leaves infested byadults, dormant stages and eggs of the red spider mite (Tetranychusurticae) were treated with a 0.05 percent aqueous emulsion of thesubstance to be tested (prepared from a 25 percent emulsifiable concentrate The test was evaluated after 6 days. The test insects werestrains of the red spider mite resistant to esters of phosphoric acid.

B) Action against ticks and their development stages 1 Rhipicephalusbursa (adults and larvae) In each case, 5 adult ticks or 50 tick larvaewere placed into a small glass test tube, and the test tubes thenimmersed for l to 2 minutes in 2 ml of an aqueous emulsion from adilution series of 100, l0, 1 and 0.] ppm of test substance. The tubeswere then sealed with a standardised cotton plug, and inverted so thatthe active-substance emulsion could be absorbed by the cotton wool, Anevaluation in the case of the adults was made after 2 weeks, and in thecase of the larvae after 3 days. There were two repeats of each test.

2) Boophilus micropulus (females and larvae) With a dilution seriesanalogous to that in Test A, tests were carried out with 5 sensitive and(DP-resistant females, respectively, or with 20 sensitive and UPresistant larvae, respectively (resistance is with respect to diazinoncompatibility). An evaluation in the case of the females was made after6 weeks, and in the case of the larvae after 3 days.

The compounds according to Example 1 were effective in these testsagainst adults and larvae of Rhipicephalus bursa and against sensitiveand ()Presistant 15 females and larvae, respectively, of Boophilusmicroplus.

EXAMPLE 4 Action against soil nematodes In order to test the actionagainst soil nematodes the active substances were added, in theconcentration stated in each case, to soil infested withroot-gallnematodes (Meloidogyne arenaria and the whole intimately mixed.In the one test series, tomato seedlings were planted immediatelyafterwards in the thus prepared soil, and in the other test seriestomatoes were planted after a waiting time of 8 days.

For an assessment of the nematicidal action, the galls present on theroots were counted 28 days after plant ing and sowing, respectively.

The active substances according to Example 1 exhibited in this test agood action against Meloidogyne arenaria.

We claim:

1. A compound of the formula wherein R represents phenyl, or phenylmonoto trisubsti tuted by halogen, monoor disubstituted by C -C alkyl, C-C -alkylthio, nitro, cyano or trifluoromethyl, or monosubstituted by C-(f carbalkoxy,

R represents methyl, methoxy, ethyl, ethoxy or phenyl,

R represents hydrogen or methyl,

R and R represent methyl, ethyl, npropyl, isopropyl or ally],

X and Y represent oxygen or sulphur. or

R and R;, with the nitrogen atom to which they are bound form themorpholino, piperidino or pyrrolidino ring, or

R;, with R or R forms a pyrrolidino or piperidino ring, whereby then thegroup R. or R not participating in the ring formation represents methylor ethyl.

2. A compound according to claim 1, wherein R I represents the groups3-methyl-4- methylthiophcnyl, 4-nitrophcnyl, 3-methyl 4- nitrophenyl,2,S-dichloro wbromophcnyl, 2,5 dichloro-4-iodophenyl. 4-methylphcnyl,2,4- dibromo-5-chlorophenyl, 2,4,5 trichlorophenyl,

3-chlorophenyl. 3-trilluoromethylphenyl, 4- methylthiophenyl,4-chlorophenyl or 4- ethyl-thionophosphoryll-formamidine according toclaim 2.

6 N,N-Diethyl-N'-[O-(3-methy|-4-methylthiophenyl)-O-ethyl-thionophosphoryl]- formamidine according toclaim 3.

7. N.N-Dimethyl-N'-[O-(2,4-dibromo-5 chlorophenyl)-()-ethyl-thionophosphoryllformamidine according to claim 2.

8. N,N-Dimethyl-N'l O-( 2,5-dichlr0-4- iodophenyl)-O-ethyl-thionophosphoryl l-formam idine according to claim 2.

9. N.N-Dimethyl-N '-l O-( 3-methyl-4- methylthiophenyl)-ethyl-thionophosphonyllformamidine according to claim 3.

l0. N.N-Dimethyl-N'-[O-(2,4.5-trichlorophenyl)-ethyl-thionophosphonyll-formamidine according to claim 2.

ll. N.N-Diethyl-N'-[O-(3-methyl-4- methylthiophenyl)-ethyl-thionophosphonyl formamidine according to claim 3.

l2.N-[O-(3-Methyl4-methylthiophenyl)-ethylthionophosphonyll-piperidyl-formimideaccording to claim 2.

l3. thionophosphonyl ]-pyrrolidinyl-formimide to claim 2.

l4. N-[O(2,4,5-Trichlorophenyll-cthylthionophosphonyll-morpholinylformimideaccording to claim 2.

l5. N,N-Dimethyl-N'-lO-(4-tolyl)-ethyl-thionophosphOnyH-formamidineaccording to claim 2.

l6. N,N-Diethyl N' [O-(4-tolyl)-ethyl-thionophosphonyH-formamidineaccording to claim 2.

l7. N N-Dimethyl-N'-lO-(3-chlorophenyl)cthylthionophosphonylLformamidineaccording to claim 2.

l8. N.N-Diethyl-N-l O-( 3-chlorophenyl)-cthylthionophosphonyll-formamidine according to claim 2.

l9.N,N-Dimcthyl-N'-[O-(4-nitrophenyl)-O-methylthionophosphoryll-formamidincaccording to claim 2.

20.N,N-Dimethyl-N'-[O(4-nitrophenyl)-O-ethylthionophosphoryll-formamidineaccording to claim 2.

21. N.N-Dimethyl-N'-[O-(3-mcthyl-4- methylthiophenyl)-O-methylthionophosphoryl formamidine according to claim 3.

22. N,N-Dimethyl-N'-[O-(2,5-dichloro-4- bromophenyl)-O-methyl-thionophosphoryl formamidine according to claim 3.

N-[O-( 2,4,5-Trichlorophenyl )-ethylaccording

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1, whereinR1 represents the groups 3-methyl-4-methylthiophenyl, 4-nitrophenyl,3-methyl-4-nitrophenyl, 2,5-dichloro-4-bromophenyl,2,5-dichloro-4-iodophenyl, 4-methylphenyl, 2,4-dibromo-5-chlorophenyl,2,4,5-trichlorophenyl, 3-chlorophenyl, 3-trifluoromethylphenyl,4-methylthiophenyl, 4-chlorophenyl or 4-cyanophenyl, R2 representsmethyl, methoxy, ethyl or ethoxy, R3 represents hydrogen, R4 and R5represent methyl or ethyl, or R4 and R5 together with the nitrogen atomto which they are bound form the morpholino, piperidino or pyrrolidinoring, X represents sulphur, and Y represents oxygen.
 3. A compoundaccording to claim 1, wherein R1 represents the3-methyl-4-methylthiophenyl group, R2 represents methyl, methoxy, ethylor ethoxy, R3 represents hydrogen, R4 and R5 represent methyl or ethyl,X represents sulphur, and Y represents oxygen.
 4. N,N-Dimethyl-N''-(O-(3-methyl-4-methylthiophenyl)-O-ethyl-thionophosphoryl) -formamidineaccording to claim
 3. 5. N,N-Dimethyl-N''-(O-(3-methyl-4-nitrophenyl)-O-ethyl-thionophosphoryl) -formamidineaccording to claim
 2. 6.N,N-Diethyl-N''-(O-(3-methyl-4-methylthiophenyl)-O-ethyl-thionophosphoryl)-formamidine according to claim
 3. 7.N,N-Dimethyl-N''-(O-(2,4-dibromo-5-chlorophenyl)-O-ethyl-thionophosphoryl)-formamidine according to claim
 2. 8.N,N-Dimethyl-N''-(O-(2,5-dichloro-4-iodophenyl)-O-ethyl-thionophosphoryl)-formamidine according to claim
 2. 9.N,N-Dimethyl-N''-(O-(3-methyl-4-methylthiophenyl)-ethyl-thionophosphonyl)-formamidine according to claim
 3. 10.N,N-Dimethyl-N''-(O-(2,4,5-trichlorophenyl)-ethyl-thionophosphonyl)-formamidine according to claim
 2. 11.N,N-Diethyl-N''-(O-(3-methyl-4-methylthiophenyl)-ethyl-thionophosphonyl)-formamidine according to claim
 3. 12.N-(O-(3-MEthyl-4-methylthiophenyl)-ethyl-thionophosphonyl)-piperidyl-formimide according to claim
 2. 13.N-(O-(2,4,5-Trichlorophenyl)-ethyl-thionophosphonyl)-pyrrolidinyl-formimideaccording to claim
 2. 14.N-(O-(2,4,5-Trichlorophenyl)-ethyl-thionophosphonyl)-morpholinyl-formimideaccording to claim
 2. 15.N,N-Dimethyl-N''-(O-(4-tolyl)-ethyl-thionophosphonyl)-formamidineaccording to claim
 2. 16.N,N-Diethyl-N''-(O-(4-tolyl)-ethyl-thionophosphonyl)-formamidineaccording to claim
 2. 17.N,N-Dimethyl-N''-(O-(3-chlorophenyl)-ethyl-thionophosphonyl)-formamidineaccording to claim
 2. 18.N,N-Diethyl-N''-(O-(3-chlorophenyl)-ethyl-thionophosphonyl)-formamidineaccording to claim
 2. 19.N,N-Dimethyl-N''-(O-(4-nitrophenyl)-O-methyl-thionophosphoryl)-formamidine according to claim
 2. 20.N,N-Dimethyl-N''-(O-(4-nitrophenyl)-O-ethyl-thionophosphoryl)-formamidine according to claim
 2. 21.N,N-Dimethyl-N''-(O-(3-methyl-4-methylthiophenyl)-O-methyl-thionophosphoryl)-formamidine according to claim
 3. 22.N,N-Dimethyl-N''-(O-(2,5-dichloro-4-bromophenyl)-O-methyl-thionophosphoryl)-formamidine according to claim 3.